US3338747A - Fuel cell system with pressure pulse generator - Google Patents

Fuel cell system with pressure pulse generator Download PDF

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Publication number
US3338747A
US3338747A US302816A US30281663A US3338747A US 3338747 A US3338747 A US 3338747A US 302816 A US302816 A US 302816A US 30281663 A US30281663 A US 30281663A US 3338747 A US3338747 A US 3338747A
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gas
pressure
electrode
electrolyte
fuel cell
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Expired - Lifetime
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US302816A
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English (en)
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Plust Heinz Gunther
Telschow Carl Georg
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BBC Brown Boveri AG Germany
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Bbc Brown Boveri & Cie
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Electrodes which are homoeoporous or have been rendered hydrophobic, and which comprise one or a plurality of strata in order to fulfill this requirement.
  • the gas required for the reaction is supplied to the electrode, for example, at constant pressure by means of a blind pipe.
  • the gas stream can be swept over the electrode at constant pressure, unreacted gas being recirculated to the electrode.
  • a reduction of this concentration gradient can be produced by difiiusion only, which on the one hand takes place slowly in the case of low-temperature cells, and on the other hand produces only an extremely incomplete leveling out in the case of heavy load conditions and a correspondingly high formation of water per unit time.
  • the over-voltage at the electrode consequently rises, involving a substantial deterioration of the electrochemical performance characteristic of the electrode.
  • the modification of the pH value of the electrolyte which occurs with the formation of water may result in poisoning of the active centres of the internal electrode surface, and thus again exert a considerable unfavourable infiuence upon the properties of the electrode.
  • the deterioration of the electrochemical properties of the electrode can also be caused by a process beginning at the gas side. This occurs when, the electrode being under heavy load, the transport of the hydrogen gas by diffusion to the triphase boundary, which is always located in the same position in the case of the electrode referred to, becomes effective for determining the speed of the electrochemical reaction. The consequence again is an increase of the over-voltage at the electrode. The same effect is caused by the presence of foreign gases in the fuel gas. The foreign gases accumulate in front of the triphase boundary'where they may produce a poisoning of the active centres. If the formation of the gas cushion becomes excessive, ultimately no further electrochemical reaction will take place in the pores. All these disadvantages arise with the conventional electrodes, irrespective "ice of whether they are operated as anode or as cathode in a fuel cell.
  • the arrangement of apparatus which has gas diffusion electrodes disposed in pairs acting as anode and as cathode and in contact with an electrolyte for the electrochemical reaction of hydrogen and oxygen or air is characterized by the fact that each gas necessary for the reaction is drawn from a reservoir and flows partially through the pores of the corresponding electrode which have a maximum diameter of a, and is fed back by a circulating device connected to the gas outlet side of the electrode to the gas inlet side of the electrode, a pressure pulse generator being arranged in the gas circuit to generate periodic pressure surges superimposed upon the pressure drop at the electrode.
  • FIG. 1 illustrates the invention diagrammatically, by the example of a single electrode of a fuel cell.
  • FIG. 2 shows an exemplary arrangement of the apparatus associated with a fuel cell.
  • FIG. 3 shows another construction of the fuel cell.
  • FIG. 4 shows a further arrangement of the apparatus.
  • the reservoir 7 serves to replace the gas which has reacted electrochemically in the electrode, and is conveniently connected to the gas circuit 6 by the control valve 8. If the electrode is operated at a specific gas pressure range having an upper and a lower limiting value, then the gas circuit 6 is charged to the upper working pressure through the valve 8. When the pressure in the gas circuit has fallen to the lower working value as a result of the electrochemical reaction, the valve 8 is again opened-for example, by means of a pressure sensitive switch not shown-until the pressure has once more attained the upper value.
  • pores are continually blown clear at the frequency of the pressure surges, and fresh equilibrium adjustments are subsequentially effected in these pores. For the majority of the pores, the dilution of the electrolyte and the formation of foreign gas cushions will not take place. In other pores, the triphase boundary is shifted to and fro by the pressure surges. Due to the shifting of the triphase boundary, the electrolyte in the pores is agitated so that it is impossible for a concentration gradient to build up in these pores.
  • a further advantage of the arrangement according to the invention is due to the fact that the reaction gas is passed in a circuit whereby total reaction of the gas is achieved with simultaneous maintenance of the optimum electrochemical properties of the electrode. Since the condition for fabricating the electrode can be met with comparatively small technological expense-the essential requirement being an upper limit of 100p. for the diameter of the pores-economic manufacture of the electrodes is insured.
  • the arrangement exhibits the advantage that the gas flowing through the electrode mixes the electrolyte in the fuel cell and favorably promotes convection of the electrolyte.
  • FIG. 2 shows an exemplary arrangement of apparatus with a fuel cell.
  • 9 designates the vessel in which the porous hydrogen electrode 10 (anode) and the porous oxygen electrode 11 (cathode) are fitted, together with their mountings (not shown) and gas conduits 12 and 13.
  • the vessel is more than half full of the electrolyte I L-for example, caustic potash solution. It is convenient to separate the anode and cathode compartments by a wall 15 impermeable to gas, which in order to reduce the internal resistance of the cell consists in the region of the electrodes of a diaphragm 16 of-for example, a finemeshed wire gauze or a porous plastic sheet connected to the electrodes.
  • the hydrogen reservoir 17 designates the hydrogen reservoir, which is connected by a control valve 18 to the gas supply conduit 12 for the hydrogen electrode.
  • the oxygen reservoir 19 is connected by the control valve 20 to the gas supply conduit 13 for the oxygen electrode.
  • the gas which has not reacted in the pores of the electrodes flows through the said pores and the electrolyte and is directed by the circulating device 22 or 24 through the gas outlet conduit 21 or 23 and back to the gas inlet side (conduit 12 or 13) of the electrodes.
  • the two gas circuits also contain the pressure pulse generators and 26, which generate pressure surges superimposed upon the pressure drop at the electrodes.
  • the circulating device 22 or 24 and the pressure pulse generator 25 or 26 need not be separate devices. It is on the contrary convenient to combine the two devices in an intermittent-acting pumpfor example, in a diaphragm pump or plunger pump.
  • One example of a suitable pulse frequency is a rate of 2.0 surges per minute.
  • the circuit is brought to the upper working pressure from the reservoir 17 or 19 through the valve 18 or 20 in the manner already described, whenever the pressure in the system falls to its lower limit.
  • the minimum pressure in the gas circuit may be chosen independently of the ambient pressure. It is convenient to determine the minimum pressure higher than the ambient pressure, because the arrangement of the gas circuit is simplified in this case.
  • the pressure in the gas circuit therefore fluctuatesfor example between 0.5 and 1 at superatmospheric pressure as minimum and maximum working pressures.
  • the water formed by the electrochemical reaction can be removed in simple manner by including a water separator 27 or 28 in each gas circuit.
  • an oxygen eliminator 2? may be arranged in the hydrogen circuit and correspondingly a hydrogen eliminator 30 in the oxygen circuit.
  • the foreign gas eliminators 31 and 32 may be provided in the gas circuits in order to eliminate other disturbing gases.
  • a further advantage of the arrangement resides in the fact that the circulating gas current removes water and heat from the electrolyte.
  • FIG. 3 shows another construction of the fuel cell.
  • the anode 10, to which hydrogen is supplied via the conduit 12, and the cathode 11, to which oxygen is supplied via the conduit 13, are in contact with the electrolyte 14 present in the vessel 9 similar to the arrangement shown in FIG. 2.
  • Above the vessel 9 are chambers 33 and 34 containing the electrolyte which surrounds the anode and cathode. These chambers 33 and 34 are connected to the vessel 9 by constricted portions 35 and 36'.
  • the gas outlet conduits 21 and 23 are connected to these chambers 33 and 34.
  • the remaining parts of the arrangement shown in FIG. 2, but not shown in FIG. 3, are located between the gas outlet conduits 21 and 23 and the gas supply conduits 11 and 13.
  • the gas rising through the electrolyte carries the electrolyte through the constricted portions 35 and 36 into the chambers 33 and 34-. From the latter, the electrolyte flows back through the conduit 37 and 38 into the vessel 3. Due to the fact that the electrolyte is passed in circuit by reason of the gas movement, thorough mixing of the electrolyte is obtained.
  • a further arrangement makes it possible for the fuel cell, which is normally provided for the generation of electrical energy, to be used for electrolysis in a simple and economical manner. If the current flow in the load circuit of the fuel element is reversed, gasi.e., hydrogen and oxygenis generated at the electrodes by electrolysis. This is the case, for example, if the fuel cell is provided to supply electric power and recuperation of energy is desired during braking.
  • Another possible application lies in the use of the fuel cell as a generator of peak load energy for delivery to an electrical supply system, so that electrical energy is delivered back to the fuel cell when the load upon the system is small.
  • the arrangement according to the invention not only prevents a pressure rise in the gas circuit during electrolysis opera tion; the gases generated are also stored and are thus available for subsequent reaction in the same fuel cell in order to generate electrical energy.
  • the gas reser voir is connected to the gas outlet side of the electrode through a first controlled valve, and a compressor is connected to the gas reservoir through a second controlled valve, the two valves being controlled by means of a pressure sensitive switch arranged on the gas outlet side in such a way that the first valve is opened when the pressure has fallen to the lower working pressure and the second valve is opened when the pressure exceeds the upper Working pressure.
  • the porous gas diffusion electrode for example, the hydrogen electrode, acting as anode in the fuel cell and is provided with a gas supply conduit 41.
  • the electrode is immersed in the electrolyte 43for example, caustic potash solutionin the vessel 42.
  • the wall 44 impermeable to gas is positioned in the centre of the vessel, and divides the anode compartment from the adjoining cathode compartmentnot shownin which the oxygen electrode is fitted.
  • the cathode compartment is further provided with the gas outlet conduit 45.
  • the electrode is connected to the external load, not shown, by the electrical conductor 46.
  • the gas which has not reacted in the pores of the electrode 40 passes through the pores, flows through the electrolyte 43 and is forced by the circuating device 47 through the gas outlet conduit 45 and fed back to the gas inlet side (conduit 41).
  • the pressure pulse generator 48 At the side of the circulating device 47 there is arranged the pressure pulse generator 48 by which the pressure surges are generated which are superimposed upon the pressure drop at the electrode and which continually blow the pores free of electrolyte.
  • the circulating device 47 and the pressure pulse generator 48 may also be combined in a single devicefor example, in a diaphragm pump or plunger pump.
  • a water separator 49, an oxygen eliminator 5t) and a foreign gas eliminator 51 are further advantageously disposed in the gas circuit.
  • a pressure sensitive switch 56 is provided, which is likewise connected to the gas outlet side of the electrode andfor examplehas contacts which are actuated for specific adjustable pressures and which actuate the valves electromagnetically by closing or opening electrical circuits.
  • Apparatus for operating a fuel cell comprising a vessel, an electrolyte in said vessel, a pair of hollow diffusion electrodes acting as an anode and a cathode in contact with said electrolyte for the electro chemical reaction of hydrogen and oxygen or air, and gasimpermeable means separating said electrodes, said vessel including outlets for the hydrogen and oxygen or air efiluent, a gas circuit for each electrode, each gas circuit communicating with one outlet of the vessel and with the interior of one of said hollow electrodes, each gas circuit including a gas circulating device including a pressure pulse generator,
  • Apparatus as defined in claim 1 comprising a gas reservoir connected to each circuit by a conduit, a pressure controlled valve in the conduit connecting each reservoir with each gas circuit, said valves being operable to maintain the gas pressure in each circuit within a predetermined range.
  • each of said pressure pulse generators is an intermittently acting pump.
  • Apparatus as defined in claim 4 comprising a chamber connected to the upper end of each compartment through a restricted passageway and a conduit connecting each chamber with the respective compartment of said vessel, said gas circuits including said chambers.
  • each gas circuit includes a water separator.
  • each gas circuit includes a foreign gas eliminator.
  • Apparatus as defined in claim 1 which comprises a gas reservoir connected to each gas circuit by a first conduit communicati g with the gas outlet side of the respective electrodes, a first gas control valve in each of said first conduits, a second conduit connecting the gas circuit of each electrode at the gas outlet side thereof with the respective gas reservoir, a second gas control valve in each of said second conduits, a compressor in each of said second conduits between said second gas control valves and said reservoirs and pressure sensitive means connected to both of said gas control valves for opening said first valve when the pressure in the gas circuit goes below a predetermined value and for opening said second valve when the pressure in the gas circuit exceeds a predetermined maximum.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
US302816A 1962-08-27 1963-08-19 Fuel cell system with pressure pulse generator Expired - Lifetime US3338747A (en)

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CH1016562A CH401179A (de) 1962-08-27 1962-08-27 Anordnung mit einem Brennstoffelement

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US3338747A true US3338747A (en) 1967-08-29

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NL (1) NL297086A (is")

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511713A (en) * 1967-02-24 1970-05-12 Gen Constr Elect Mec Fuel cell with a basic electrolyte having continuous automatic decarbonization, and method of generating electricity therewith
US3525643A (en) * 1966-04-13 1970-08-25 Anita Ryhiner Process for producing electrical energy in a fuel cell
US3527618A (en) * 1968-05-13 1970-09-08 United Aircraft Corp Fuel cell with carbon dioxide gas stripper and method of operation
US3653969A (en) * 1966-05-09 1972-04-04 Gen Electric Fuel cell system with plural fuel cells
EP0103069A3 (en) * 1982-09-09 1985-12-11 Varta Batterie Aktiengesellschaft Method and apparatus for the electrolyte circulation in electric accumulators by means of force pumps
US6093502A (en) * 1998-10-28 2000-07-25 Plug Power Inc. Fuel cell with selective pressure variation and dynamic inflection
WO2003105259A3 (en) * 2002-06-10 2005-04-21 Hewlett Packard Development Co REAGENT FUEL CELL SUPPLY
WO2004113590A3 (en) * 2003-06-24 2005-08-11 Mario Melosi Electrochemical thermodynamo
EP1284514A3 (en) * 2001-08-16 2007-01-24 Asia Pacific Fuel Cell Technologies, Ltd. Anode stream recirculation system for a fuel cell
ITMI20090243A1 (it) * 2009-02-20 2010-08-21 Henergy Srl Elettrodo poroso con trasporto di gas e di elettrolita
US20220145479A1 (en) * 2019-02-01 2022-05-12 Aquahydrex, Inc. Electrochemical system with confined electrolyte
US20240197546A1 (en) * 2020-03-25 2024-06-20 Daio Paper Corporation Attachable-type disposable wearing article

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US668838A (en) * 1899-07-19 1901-02-26 Etude Des Piles Electr Soc D Voltaic battery.
US2947797A (en) * 1956-05-18 1960-08-02 Ruhrchemie Ag Direct production of electrical energy from combustible fuel gases
CA616031A (en) * 1961-03-07 Justi Eduard Process for the storage of electrical energy
US3002039A (en) * 1957-05-03 1961-09-26 Nat Res Dev Electrical batteries
US3014976A (en) * 1960-02-29 1961-12-26 Gen Electric Fuel cell system with means for prevention of damage by differential gas pressures
US3133837A (en) * 1959-12-31 1964-05-19 Electric Storage Battery Co Fuel cell system
US3198664A (en) * 1961-11-30 1965-08-03 United Aircraft Corp Fuel cell system

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA616031A (en) * 1961-03-07 Justi Eduard Process for the storage of electrical energy
US668838A (en) * 1899-07-19 1901-02-26 Etude Des Piles Electr Soc D Voltaic battery.
US2947797A (en) * 1956-05-18 1960-08-02 Ruhrchemie Ag Direct production of electrical energy from combustible fuel gases
US3002039A (en) * 1957-05-03 1961-09-26 Nat Res Dev Electrical batteries
US3133837A (en) * 1959-12-31 1964-05-19 Electric Storage Battery Co Fuel cell system
US3014976A (en) * 1960-02-29 1961-12-26 Gen Electric Fuel cell system with means for prevention of damage by differential gas pressures
US3198664A (en) * 1961-11-30 1965-08-03 United Aircraft Corp Fuel cell system

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3525643A (en) * 1966-04-13 1970-08-25 Anita Ryhiner Process for producing electrical energy in a fuel cell
US3653969A (en) * 1966-05-09 1972-04-04 Gen Electric Fuel cell system with plural fuel cells
US3511713A (en) * 1967-02-24 1970-05-12 Gen Constr Elect Mec Fuel cell with a basic electrolyte having continuous automatic decarbonization, and method of generating electricity therewith
US3527618A (en) * 1968-05-13 1970-09-08 United Aircraft Corp Fuel cell with carbon dioxide gas stripper and method of operation
EP0103069A3 (en) * 1982-09-09 1985-12-11 Varta Batterie Aktiengesellschaft Method and apparatus for the electrolyte circulation in electric accumulators by means of force pumps
US6093502A (en) * 1998-10-28 2000-07-25 Plug Power Inc. Fuel cell with selective pressure variation and dynamic inflection
EP1284514A3 (en) * 2001-08-16 2007-01-24 Asia Pacific Fuel Cell Technologies, Ltd. Anode stream recirculation system for a fuel cell
US7122257B2 (en) 2002-06-10 2006-10-17 Hewlett-Packard Development Company, Lp. Fuel cell reactant supply
WO2003105259A3 (en) * 2002-06-10 2005-04-21 Hewlett Packard Development Co REAGENT FUEL CELL SUPPLY
WO2004113590A3 (en) * 2003-06-24 2005-08-11 Mario Melosi Electrochemical thermodynamo
US20070080069A1 (en) * 2003-06-24 2007-04-12 Mario Melosi Electrochemical thermodynamo
US8034220B2 (en) 2003-06-24 2011-10-11 Paolo Ricotti Electrochemical thermodynamo
ITMI20090243A1 (it) * 2009-02-20 2010-08-21 Henergy Srl Elettrodo poroso con trasporto di gas e di elettrolita
US20220145479A1 (en) * 2019-02-01 2022-05-12 Aquahydrex, Inc. Electrochemical system with confined electrolyte
US12080928B2 (en) 2019-02-01 2024-09-03 Edac Labs, Inc. Electrochemical system with confined electrolyte
US20240197546A1 (en) * 2020-03-25 2024-06-20 Daio Paper Corporation Attachable-type disposable wearing article

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BE636538A (is")
NL297086A (is")
CH401179A (de) 1965-10-31

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